Synthesis and structural characterization of seven copper(I) complexes with 3-amino-5,6-dimethyl-1,2,4-triazine and triphenylphosphine/triphenylarsine

Article abstract of DOI:10.1016/j.poly.2013.12.026

Seven new copper(I) complexes containing 3-amino-5,6-dimethyl-1,2,4- triazine (ADMT), [Cu(μ-Cl)(ADMT)(PPh₃)]₂ (1), [Cu(μ-NCS)(ADMT)(PPh₃)]₂ (2), [Cu(ADMT)(PPh ₃)₂Cl] (3), [Cu(ADMT)(PPh₃)₂Br] (4), [Cu(μ-Cl)(ADMT)(AsPh₃)]₂ (5), [Cu(μ-Br)(ADMT) (AsPh₃)]₂ (6) and [Cu(ADMT)(AsPh₃) ₂I] (7) have been synthesized by the reactions of CuX (X = Cl, Br, I, SCN) with triphenylphosphine/triphenylarsine EPh₃ (E = P for 1-4; E = As for 5-7) and ADMT in mixed solvents. Complexes 1-7 have been characterized by IR, NMR, luminescence, elemental analyses and X-ray diffraction. In 1, 2, 5 and 6, the intermolecular hydrogen bonds of type I R₂²(8) are formed by two N-H donors and two N atoms from two ADMT ligands. In 1-7, the intramolecular hydrogen bond of type II R₁¹(6) is formed between one N-H donor from ADMT and one halide ion. In 1, 2, 5 and 6, the halide ions and thiocyanate ions bridge two copper atoms to form the parallelogram Cu₂X₂, which are further linked to form infinite zigzag chains along a-axis through the hydrogen bond of type I R₂ ²(8).

Full text of DOI:10.1016/j.poly.2013.12.026

Polyhedron 70 (2014) 65–70
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and structural characterization of seven copper(I) complexes
with 3-amino-5,6-dimethyl-1,2,4-triazine and triphenylphosphine/
triphenylarsine
a
a
Jian-Bao Li a, Rong Wang a, Min Liu b, Man-Hua Wu a, Qiong-Hua Jin a, , Zhong-Feng Li , Han-Qin Tang ,
⇑
Jin-Zhao Xiang a, Mei-Song Guo a, Ge Song a
a Department of Chemistry, Capital Normal University, Beijing 100048, China
b The College of Materials Science and Engineering, Beijing University of Technology, Beijing 100022, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Seven new copper(I) complexes containing 3-amino-5,6-dimethyl-1,2,4-triazine (ADMT), [Cu(l-
Received 25 October 2013
Accepted 23 December 2013
Available online 31 December 2013
Cl)(ADMT)(PPh3)]2 (1), [Cu(
l
-NCS)(ADMT)(PPh3)]2 (2), [Cu(ADMT)(PPh3)2Cl] (3), [Cu(ADMT)(PPh3)2Br]
(4), [Cu( -Cl)(ADMT)(AsPh3)]2 (5), [Cu(
l
l
-Br)(ADMT)(AsPh3)]2 (6) and [Cu(ADMT)(AsPh3)2I] (7) have been
synthesized by the reactions of CuX (X = Cl, Br, I, SCN) with triphenylphosphine/triphenylarsine EPh3
(E = P for 1–4; E = As for 5–7) and ADMT in mixed solvents. Complexes 1–7 have been characterized
by IR, NMR, luminescence, elemental analyses and X-ray diffraction. In 1, 2, 5 and 6, the intermolecular
hydrogen bonds of type I R22(8) are formed by two N–H donors and two N atoms from two ADMT ligands.
In 1–7, the intramolecular hydrogen bond of type II R11(6) is formed between one N–H donor from ADMT
and one halide ion. In 1, 2, 5 and 6, the halide ions and thiocyanate ions bridge two copper atoms to form
the parallelogram Cu2X2, which are further linked to form infinite zigzag chains along a-axis through the
hydrogen bond of type I R22(8).
Keywords:
Copper (I) complex
3-Amino-5,6-dimethyl-1,2,4-triazine
Triphenylphosphine
Triphenylarsine
Luminescent
Crystal structure
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction
These inorganic fragments can be linked together by bridging
ligands to form 1D-3D extended organic–inorganic hybrid archi-
The study on organic and inorganic molecules is of current
interest because of their interesting coordination chemistry and
potential application in gas absorption and separation, catalysis,
and the development of electronic, optical, magnetic, and sensing
materials [1–7]. In organic–inorganic hybrid molecules, group 11
metals usually serve as versatile connecting nodes. Their structures
are often controlled by metal–ligand interaction, weak d10–d10
metallophilic interaction [8], intermolecular hydrogen bonds [9]
tectures [11]. Among numerous multi-functional ligands, 3-Ami-
no-5,6-dimethyl-1,2,4-triazine (ADMT) is a good candidate as the
main ligand because its triazine ring is capable of coordinating to
metal atom, and its amino group may form hydrogen bonds with
other acceptors. We speculate that this ligand, just as 2-AMP,
may be used as a building block to form di-, poly-nuclear or supra-
molecular organic–inorganic hybrid molecules [12]. In our previ-
ous work, we found that the existence of organophosphorous
ligands can facilitate the synthesis of group 11 metal complexes
with novel structures [13–14]. Here we select EPh3 (E = P, As) as
the coligand. Finally, we choose mixed solvent since it is usually
helpful to improve the crystal quality for group 11 metal com-
plexes of N- and P-donor ligands.
and
p–p packing interactions [10]. As far as we know the Cu(I)
supramolecular complexes formed by hydrogen bonds are difficult
to synthesize because of the insolubility of Cu(I) salts in organic
solvent and their instability in water and air. To synthesize this
kind of complexes, we need to find a suitable main organic ligand
that can form inter- or intramolecular hydrogen bonds with other
acceptors as well as coligand which can enhance the stability of
Cu(I) complexes.
In this work, we select copper(I) halides as inorganic units be-
cause CuX possesses the self-assembly capability to form different
kinds of inorganic units, such as Cu2X2 dimers, Cu4X4 cubic tetra-
mers, (Cu2X2)n stair-step polymers and (CuX)n chain polymers.
In this paper, we report seven new copper(I) complexes [Cu(
Cl)(ADMT)(PPh3)]2 (1), [Cu( -NCS)(ADMT)(PPh3)]2(2), [Cu(ADMT)
(PPh3)2Cl] (3), [Cu(ADMT)(PPh3)2Br] (4), [Cu( -Cl)(ADMT)(AsPh3)]2
(5), [Cu( -Br)(ADMT)(AsPh3)]2 (6) and [Cu(ADMT)(AsPh3)2I] (7)
l-
l
l
l
obtained by the reactions of CuX (X = Cl, Br, I, SCN) with EPh3
(E = P for 1–4; E = As for 5–7) and ADMT in the mixed solvent. 1,
2, 5 and 6 are dinuclear complexes with infinite zigzag chain
structure. In 1, 5 and 6, the chain is formed by the intermolecular
hydrogen bonds R22(8) and intramolecular hydrogen bond R11(6)
N–HÁÁÁX (X = Cl, Br) (Scheme 1) while in 2 only intermolecular
⇑
Corresponding author. Tel.: +86 10 68903033; fax: +86 10 68902320.
E-mail address: jinqh@mail.cnu.edu.cn (Q.-H. Jin).
0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.12.026

66
J.-B. Li et al. / Polyhedron 70 (2014) 65–70
hydrogen bonds R22(8) exist. 3, 4 and 7 are mononuclear com-
plexes. In 3 and 4, there only exist intramolecular hydrogen bonds
N-HÁÁÁX (X = Cl, Br). In 7, there only exist intermolecular hydrogen
bonds R22(8) which make it a dimer. Up to date, the hydrogen
bonds N–HÁÁÁX (X = Cl, Br) have been reported in Cu(II) complexes
of 2-aminopyrimidine [15] and Ru(II) complexes of biimidazole
[16–17]. However, to our knowledge, the hydrogen bond N-HÁÁÁX
in Cu(I) complex hasn’t been reported, which makes these com-
plexes more intriguing.
C, 56.69; H, 4.56; N, 13.78%. IR(cmÀ1, KBr pellets): 3436 m, 2099s,
1635 m, 1482 m, 1434s, 742s, 694s, 523s.
2.2.3. Synthesis of [Cu(ADMT)(PPh3)2Cl] (3)
Complex 3 was prepared in a manner similar to that described
for 1 except that the mole of PPh3 was doubled (1.5740 g,
0.6 mmol). Yield: 82%. Anal. Calc. for C41H38ClCuN4P2: C, 65.88; H,
5.13; N, 7.45. Found: C, 65.80; H, 5.08; N, 7.49%. IR(cmÀ1, KBr pel-
lets): 3421 m, 3163w, 3052w, 1638 m, 1479 m, 1434 m, 1396 m,
1185w, 1094 m, 1026w, 788w, 746s, 695s, 514s, 435w.
2. Experimental
2.2.4. Synthesis of [Cu(ADMT)(PPh3)2Br] (4)
Complex 4 was prepared in a manner similar to that described
for 3, using CuBr (0.0430 g, 0.3 mmol), PPh3 (1.5740 g, 0.6 mmol)
and ADMT (0.0372 g, 0.3 mmol) as starting materials. Yield: 85%.
Anal. Calc. for C41H38BrCuN4P2: C, 62.18; H, 4.83; N, 7.07. Found:
C, 62.11; H, 4.79; N, 7.07%. IR(cmÀ1, KBr pellets): 3424 m, 3160w,
3050w, 1636 m, 1473 m, 1425 m, 1396 m, 1189w, 1094 m,
1026w, 999w, 747s, 696s, 509s, 492w, 437w.
2.1. Materials and measurements
All chemical reagents are commercially available and used
without furthermore treatment. FT-IR spectra (KBr pellets) were
measured on a Perkin-Elmer Infrared spectrometer. C, H and N ele-
mental analysis were carried out on a Elementar Vario MICRO
CUBE(Germany) elemental analyzer. Room-temperature fluores-
cence spectra were measured on F-4500 FL Spectrophotometer.
1H NMR and 31P NMR were recorded at room temperature with a
Bruker DPX 600 spectrometer.
2.2.5. Synthesis of [Cu (l-Cl)(ADMT)(AsPh3)]2 (5)
Complex 5 was prepared in a manner similar to that described
for 1, using CuCl (0.0297 g, 0.3 mmol), triphenylarsine (AsPh3)
(0.0919 g, 0.3 mmol) and ADMT (0.0372 g, 0.3 mmol) as starting
materials. Yield: 70%, Anal. Calc, for C46H46Cu2N8Cl2 As2: C, 52.18;
2.2. Preparation of the complexes
H, 4.38; N, 10.58. Found: C, 52.14; H, 4.35; N, 10.55%. IR (cmÀ1
,
2.2.1. Synthesis of [Cu(l-Cl)(ADMT)(PPh3)]2 (1)
KBr pellets): 3302 m, 3163 m, 3067w, 1649s, 1569 m, 1527w,
1499 m, 1482w, 1435 m, 1396 m, 1309w, 1186w, 1133w, 1026w,
999w, 962w, 787w, 741s, 695s, 551w, 474 m, 434w.
A mixture of CuCl(0.0297 g, 0.3 mmol), triphenylphosphine
(PPh3) (0.7870 g, 0.3 mmol) and 3-Amino-5,6-dimethyl-1,2,4-tri-
azine (ADMT) (0.0372 g, 0.3 mmol) were dissolved in a mixture
of 7 ml CH2Cl2 and 3 ml MeOH, stirred for 3 h and filtered. Yellow
crystal 1 was obtained from the filtrate after standing at the room
temperature for several days. Yield: 75%. Anal. Calc. for C46H46Cu2-
N8Cl2P2: C, 56.95; H, 4.67; N, 11.54. Found: C, 56.88; H, 4.74; N,
11.49%. IR(cmÀ1, KBr pellets): 3440 m, 3159w, 3052w, 1616s,
1566w, 1480 m, 1434s, 1397w, 1095w, 1026w, 999w, 745s, 695s,
515 m, 503w, 437w.
2.2.6. Synthesis of [Cu (l-Br)(ADMT)(AsPh3)]2 (6)
Complex 6 was prepared in a manner similar to that described
for 1, using CuBr (0.0430 g, 0.3 mmol), AsPh3 (0.0919 g, 0.3 mmol)
and ADMT (0.0372 g, 0.3 mmol) as starting materials. Yield: 46%,
Anal. Calc, for C46H46Cu2N8Br2As2: C, 48.14; H, 4.04; N, 9.76. Found:
C, 48.11; H, 4.02; N, 9.74%. IR (cmÀ1, KBr pellets):3441 m, 3051w,
1633 m, 1586w, 1483 m, 1435 m, 1397w, 1086w, 1077w, 1024w,
999w, 783s, 695s, 527w, 480w.
2.2.2. Synthesis of [Cu(l-NCS)(ADMT)(PPh3)]2 (2)
Complex 2 was prepared in a manner similar to that described
for 1, using CuSCN (0.0365 g, 0.3 mmol), PPh3 (0.0787 g, 0.3 mmol)
and ADMT (0.0372 g, 0.3 mmol) as starting materials. Yield: 21%.
Anal. Calc. for C48H46Cu2N10P2S2: C, 56.78; H, 4.48; N, 13.84. Found:
2.2.7. Synthesis of [Cu(ADMT)(AsPh3)2I] (7)
A
mixture of CuI (0.0568 g, 0.3 mmol), ADMT (0.0372 g,
0.3 mmol) and N,N-dimethylformamide (DMF) (3 ml) was stirred
for 20 min at room temperature. By adding the solution of CH2Cl2
Scheme 1. The intermolecular hydrogen bond of type I R22(8) and the intramolecular hydrogen bond of type II R11(6).

J.-B. Li et al. / Polyhedron 70 (2014) 65–70
67
(7 ml) containing AsPh3 (0.0919 g, 0.3 mmol) into the reaction sys-
tem after stirring for another 20 min, and filtered, crystal 7 was ob-
tained from the filtrate after standing at the room temperature for
several days. Yield: 34%. Anal. Calc. for C41H38Cu1N4IP2: C,53.12; H,
4.13; N, 6.04. Found: C, 53.10; H, 4.11; N, 6.02%. IR(cmÀ1, KBr pel-
lets): 3308 m, 3162w, 1648s, 1566 m, 1526w, 1496w, 1483 m,
1435 m, 1395 m, 1135w, 1078w, 1025w, 962w, 787w, 740s,
695s, 635w, 534w, 474w.
the mixed solvent of CH2Cl2/MeOH, CH2Cl2/CH3CN or CH2Cl2 /DMF.
But no crystal suitable to be determined was obtained. One possi-
ble reason is that the big radius of IÀ makes the intramolecular
hydrogen bond N–H. . .I too weak to be effective.
3.2. Single crystal X-ray studies
3.2.1. Complex [Cu(l-Cl)(ADMT)(PPh3)]2 (1)
Compound 1 consists of inversion symmetric dimers with a dia-
mond-shaped Cu2Cl2 group at the center. In the plane, the Cu. . .Cu
distance of 3.354(8) Å is longer than the sum of van der Waals radii
of two copper atoms (2.800 Å), indicating that there is no metal–
metal bonding interaction in the title complex. Each copper atom
is coordinated by one P atom from PPh3, two Br atoms and one N
atom from ADMT (Fig. 1a). The angles around Cu are in the range
96.8(9)–129.1(5)°, which indicates that the geometry around Cu
is a distorted tetrahedron. The mean bond distances of Cu–Cl and
Cu–P are 2.463(1) Å and 2.197(1) Å respectively, which are similar
2.3. X-ray crystallographic study of complexes
Single crystals of the title complexes were mounted on a Bruker
Smart 1000 CCD diffractometer equipped with a graphite-mono-
chromated Mo K
a (k = 0.71073 Å) radiation at 293(2) K. Semi-
empirical absorption corrections were applied using SABABS pro-
gram. All the structures were solved by direct methods using SHELXS
program of the SHELXTL-97 package and refined with SHELXL-97[18–
19]. Metal atom centers were located from the E-maps and other
non-hydrogen atoms were located in successive difference Fourier
syntheses. The final refinements were performed by full matrix
least-squares methods with anisotropic thermal parameters for
non-hydrogen atoms on F2. The hydrogen atoms were generated
geometrically and refined with displacement parameters riding
on the concerned atoms. Further crystallographic data and experi-
mental details for structural analyses of complexes 1–7 are sum-
marized in Table S1. The selected bond lengths and angles, and
hydrogen bond lengths and angles of 1–7 are given in Table S2.
to those observed in [Cu(
l-Cl)(2-Apy)(PPh3)]2 [20] and [(PPh3)2-
Cu2( -Cl)2( -4,4’-bipyridine)] [21]. The angles of Cl-Cu-Cl and
l
l
Cu–Cl -Cu are 92.6(4)° and 87.4(4)°, which are close to those found
in the two complexes previously mentioned. The angles Cl(1)A-
Cu(1)-Cl(1) and Cu(1)A-Cl(1)-Cu(1) [92.6(4)° and 87.4(4)°] are
equal to the angles Cl(1)A-Cu(1)A-Cl(1) and Cu(1)-Cl(1)A-Cu(1)
respectively. The sum of the internal angles of the four-member
ring [-Cu-Cl-Cu-Cl-] in the Cu2Cl2 core are 360°, which indicates
3. Results and discussion
3.1. Synthesis of complexes 1–7
The reactions of preparing complexes 1–7 are summarized in
Scheme 2. To obtain these seven mixed-ligand compounds, it is
important to take into account the ratio of starting materials, the
choice of the solvent, the property of counter anions and the reac-
tion time.
Compounds 1–6, were prepared by treatment of CuX, EPh3 with
ADMT in proper mole ratio (1:1:1 for 1, 2, 5, 6 and 1:2:1 for 3, 4) in
the mixed solvent of CH2Cl2 and MeOH. Complex 7 was obtained
by the reaction of CuI, AsPh3 with ADMT in mole ratio 1:1:1 in
the mixed solvent of CH2Cl2 and DMF. The reaction time for syn-
thesis of compounds 1–6 is 3 h while that for compound 7 is short-
ened to 20 min. 1–7 are insoluble in diethyl ether but soluble in
methanol, ethanol, acetonitrile, chloroform, N,N-dimethylformam-
ide and dimethylsulfoxide.
In order to obtain a full series of complexes, we have studied the
reactions of CuI, PPh3 with ADMT in either ratio 1:1:1.5 or 1:1:2 in
Fig. 1. (a) ORTEP diagram of compound 1 together with the atomic numbering
scheme. Thermal ellipsoids drawn at the 50% probability level, hydrogen atoms are
omitted for clarity. (b) Perspective view of the infinite zigzag chains of 1, hydrogen
atoms of methyl are omitted for clarity.
Scheme 2. The routine of synthesis for complexes 1–7.

68
J.-B. Li et al. / Polyhedron 70 (2014) 65–70
that the ringis a parallelogram. In each molecule of compound 1,
Compound 3 is mononuclear (Fig. 3). The copper(I) atom is
coordinated by one nitrogen atom of ADMT with the Cu–N distance
of 2.138(4) Å, one Cl atom with the Cu–Cl distance of 2.383(1) Å
and two phosphorus atoms with the Cu–P distance of 2.279(1)-
2.280(1) Å, forming a distorted tetrahedron geometry. The geomet-
rical distortion from ideal angles can be attributed to the need to
accommodate the bulky triphenylphosphine groups. The bond
length of Cu-P is slightly longer than those values founded in com-
plexes [Cu(pym2S)(PPh3)2] (2.242(7)À2.256(7) Å) [24] and
[Cu(tsac)(PPh3)2] (2.250(8)À2.266(8) Å) [25]. The distance of
H(2B). . .Cl(1) is 2.568 Å and the angle N(2)-H(2B). . .Cl (1) is
165.8° in the intramolecular hydrogen bond formed by the amino
group and the chloride ion.
the intramolecular hydrogen bond R11(6) is formed by one Cl atom
and one N–H group from ADMT. Two adjacent [Cu(l-
Cl)(ADMT)(PPh3)]2 units are connected via intermolecular hydro-
gen bond R22(8) formed by two amino groups and two N atoms
from two ADMT ligands, resulting in a infinite zigzag chain
(Fig. 1b). Distances for these N–H. . .L(L = Cl, N) hydrogen bonds
(H(4A). . .Cl(1)=2.349 Å, H(4B). . .N(3)=2.149 Å) and the angles
(Cl(1). . .H(4A)-N(4)=171.5°, N(3). . .N(4)-H(4B)=173.9°) show that
the N–H. . .L segments are close to linearity.
3.2.2. Complex [Cu(l-NCS)(ADMT)(PPh3)]2 (2)
The crystal structure consists of dimeric units [CuNCS(PCH3(C6-
H5)2)2] with a Cu-Cu distance of 5.286(8) Å and a symmetry center
between two copper atoms. As can be seen in Fig. 2, the two copper
atoms are bridged by two thiocyanates to form an eight-membered
ring which is approximately planar. The deviation from planarity is
about 0.290 Å, which is determined by two thiocyanate anions.
Similar atomic arrangements were observed in the structures of
3.2.4. Complex [Cu(l-Br)(ADMT)(AsPh3)]2 (6)
Complex 6 is triclinic in P-1 space group. The perspective view
of compound is similar to complex 1. Each copper(I) atom is coor-
dinated by one N atom from ADMT, one As atom from AsPh3 and
two bromine atoms to form a distorted tetrahedron (Fig. 4). The
Cu. . .Cu distance of 3.311 Å is longer than the sum of covalent radii,
which shows that there is no metal–metal bonding interaction. The
Cu–N distance of 2.065(5) Å is close to those in 1, but longer than
those in 2. The Cu–As distance of 2.350(1) Å is similar to those
founded in [(PhMe2As)2CuCl]2 [2.360(1) Å] [26] and [(Ph3As)2-
[AgSCNP(n-C3H7)3] [22] and
a-[Pt2(SCN)2C12(P(C3H7)3)2] [23], but
in these cases the deviation of the eight-membered ring from pla-
narity is considerably smaller.
Each copper atom is surrounded by one phosphorus atom, one
sulfur atom and two nitrogen atoms. The Cu-P bond length of
2.212(1) Å and the Cu–N distance of 2.089(4) Å are normal for
these types of coordinated ligands. The Cu–S bond length of
2.538(2) Å is longer than the normal Cu-S single bond of 2.390 Å.
Cu(
bond length of Cu-Br is longer than the similar bond value
found in [(Ph3As)(MeCN)Cu( -Br)2Cu(NCMe)(AsPh3)] [2.457(9)–
l-Cl)2Cu(NCMe)(AsPh3)] [2.353(2)–2.355(2) Å] [27]. The mean
l
2.529(1) Å] [27]. The sum of the internal angles of the Cu2X2 core
is 360°, which shows that this four-member ring [-Cu-X-Cu-X-] is
coplanar.
Two adjacent [Cu(l-SCN)(ADMT)(PPh3)]2 units are connected via
intermolecular hydrogen bond R22(8) formed by two amino groups
and two N atoms from two ADMT, resulting in a infinite zigzag
Similar to compound 1, in each [Cu(l-Br)(ADMT)(AsPh3)]2 unit,
chain.
Distance
of
the
N–H. . .N
hydrogen
bond
the intramolecular hydrogen bond of type II R11(6) is formed be-
tween one N-H donor from ADMT and one bromine atom. Two
(H(4B). . .N(3)=2.149 Å) and the angle (N(3). . .N(4)-H(4B)=173.9°)
show that the N–H. . .N segments are close to linearity.
adjacent [Cu(
to each other via the intermolecular hydrogen bond of type I
R22(8) resulting in
infinite zigzag chain along the a-axis
l-Br)(ADMT)(AsPh3)]2 units are further connected
3.2.3. Complex [Cu(ADMT)(PPh3)2Cl] (3)
a
Because the complexes 3 and 6 are isostructural to 4 and 5
respectively, only the structures of 3 and 6 will be described. The
molecular structures of compounds 4 and 5 are showed in
Fig. S1–S3.
(Fig. 4b). The angles N–H. . .L [L = N or Br] are close to 180°, which
demonstrate that these N–H. . .L fragments are nearly linear.
3.2.5. Complex [Cu(ADMT)(AsPh3)2I] (7)
Complex 7 is a mononuclear compound and its crystal is mono-
clinic in space group P2(1)/c. The perspective view of 7 is similar to
Fig. 2. ORTEP diagram of compound 2 together with the atomic numbering scheme.
Thermal ellipsoids drawn at the 50% probability level, hydrogen atoms are omitted
for clarity.
Fig. 3. ORTEP diagram of compound 3 together with the atomic numbering scheme.
Thermal ellipsoids drawn at the 50% probability level, hydrogen atoms are omitted
for clarity.

J.-B. Li et al. / Polyhedron 70 (2014) 65–70
69
Fig. 4. (a) ORTEP diagram of compound 6 together with the atomic numbering
scheme. Thermal ellipsoids drawn at the 50% probability level, hydrogen atoms are
omitted for clarity. (b) Perspective view of the infinite zigzag chains of 6, hydrogen
atoms of methyl are have been omitted.
Fig. 5. (a) ORTEP diagram of compound 7 together with the atomic numbering
scheme. Thermal ellipsoids drawn at the 50% probability level, hydrogen atoms are
omitted for clarity. (b) Perspective view of a dimer in 7.
that of compound 3 (Fig. 5a). Each copper(I) is coordinated by one
nitrogen atom from ADMT with the Cu–N distance of 2.096(3) Å,
one I atom with the Cu-I distance of 2.617(5) Å, two arsenic atoms
from AsPh3 with the Cu-As distance of 2.397(6)–2.401(6) Å to form
a distorted tetrahedron. The bond length of Cu-N is shorter than
that in 3, but it is longer than those in 1, 2, 4–6. Just as in 3, the
geometrical distortion from ideal angles can also be attributed to
the need to accommodate the bulky triphenylarsine groups. Sur-
prisingly, although all of 3, 4 and 7 are mononuclear complexes,
7 is a dimer generated by intermolecular hydrogen bonds R22(8)
formed by two amino groups from two ADMT ligands with the dis-
tance N(3). . .N(4) of 3.106 Å (Fig. 5b).
In these complexes, the hydrogen bonds are very important to
form their structures. The effective intramolecular and intermolec-
ular hydrogen bonds in 1–7 help to stabilize the Cu(I) complexes
and control the structures of complexes. And infinite zigzag chains
are formed in 1, 2, 5 and 6 by the intermolecular hydrogen bond
R22(8). Through the intermolecular hydrogen bond of type I
R22(8), the dimer structure is formed in 7. Compounds 3 and 4
are of monomer structure formed by intramolecular hydrogen
bond of type II R11(6).
state photoluminescence properties of complexes 1–7were investi-
gated at room temperature. The fluorescence emissions are dis-
played in Fig. S4–S6. When these complexes are excited at
337 nm (for 1), 379 nm (for 2), 378 nm (for 3), 341 nm (for 4),
340 nm (for 5), 345 nm (for 6), 340 nm (for 7), they all display
strong fluorescence effect, and their emission peaks are at
409 nm (for 1), 442 nm (for 2), 440 nm (for 3), 408 nm (for 4 and
6), 429 nm (for 5), 407 nm (for 7). The above data indicate that
excitation and emission spectra of 1–7 are similar. For ADMT, only
a weak fluorescence spectra could be observed and its emission
fluorescence spectra peak is at 344 nm (Ex = 284 nm). And the li-
gand EPh3 (E = P, AS) exhibits fluorescence signal centered at
450 nm with an excitation maximum at 435 nm. Its emission can
be assigned to
p?
p⁄ electron transition. The intense emission
maximum peaks of complexes 1–7 appeared at the range of
407 nm–442 nm may be attributed to the intraligand charge trans-
fer (ILCT) based on PPh3 [30].The kmax values of mononuclear com-
plexes 3–4 are in the order 4 < 3, and the kmax values of dinuclear
complexes 5–6 are in the order 6 < 5, which is consistent with
the order of ligand field strength of the halide ions in the com-
plexes (Br- < ClÀ) [31].
3.3. Luminescent Properties
3.4. NMR spectra of complexes
Photoluminescence properties of coordination d10metal com-
plexes have been widely investigated with the purpose of develop-
ing light-emitting materials and devices. [28–29] Hence, the solid
The 1H NMR spectra of complexes 1–7 and 31P NMR spectra of
complexes 1–4 have been measured in CDCl3 solution at room

70
J.-B. Li et al. / Polyhedron 70 (2014) 65–70
temperature. The resonance signals at range 7.1–7.4 ppm are as-
signed to the protons of PPh3 and AsPh3 in the solution of 1–7.
The signals of aromatic protons of PPh3 and AsPh3 for 1–7 are in
the range of 7.2–7.4 ppm, 7.2–7.4 ppm, 7.2–7.4 ppm, 7.1–
7.4 ppm, 7.2–7.4 ppm, 7.2–7.3 ppm, 7.3–7.4 ppm, which indicates
that the environment of the ligand PPh3 and AsPh3 in these seven
is similar. The signals of NH in ligand C5H8N4 in 1–7 are similar.
The signals of C5H8N4 ligand are at 5.3–5.9 ppm. (singlet peak).
In 31P NMR spectra of 1–4, all phosphorus atoms in each mole-
cule are chemically equivalent because only a single resonance sig-
nal is found for each complex (À2.48 ppm for 1, À4.16 ppm for 3,
À3.56 ppm for 4). The similarity of resonance signals in solution
of 1–4 shows that the chemistry environment for the phosphorus
atom from PPh3 in 1–4 is similar.
free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/
j.poly.2013.12.026.
References
[1] J.L.C. Rowsell, O.M. Yaghi, J. Am. Chem. Soc. 128 (2006) 1304.
[2] M. Pellei, G.G. Lobbia, C. Santini, R. Spagna, M. Camalli, D. Fedeli, G. Falcioni,
Dalton Trans. 17 (2004) 2822.
[3] J.Y. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Chem. Soc.
Rev. 38 (2009) 1450.
[4] R. Kuhlman, G.L. Schimek, J.W. Kolis, Polyhedron 18 (1999) 1379.
[5] M. Henary, J.L. Wootton, S.I. Khan, J.I. Zink, Inorg. Chem. 36 (1997) 796.
[6] Y.Z. Tang, X.S. Wang, T. Zhou, R.G. Xiong, Cryst. Growth Des. 6 (2006) 11.
[7] B. Chen, L. Wang, F. Zapata, G. Qian, E.B. Lobkovsky, J. Am. Chem. Soc. 130
(2008) 6718.
4. Conclusion
[8] Q.H. Jin, L.L. Zhou, L.J. Xu, Y.Y. Zhang, C.L. Zhang, X.M. Lu, Polyhedron 29 (2010)
317.
[9] J. Hamblin, S.P. Argent, A.J. Blake, C. Wilson, N.R. Champness, CrystEngComm.
10 (2008) 1782.
[10] L. Carlucci, G. Cinai, D.M. Proserpio, J. Coord. Chem. Rev. 246 (2003) 247.
[11] P.M. Graham, R.D. Pike, Inorg. Chem. 39 (2000) 5121.
[12] Y.H. Wang, K.L. Chu, H.C. Chen, C.W. Yeh, Z.K. Chan, M.C. Suen, J.D. Chen, J.C.
Wang, CrystEngComm. 8 (2006) 84.
[13] L.L. Song, Q.H. Jin, L.N. Cui, C.L. Zhang, Inorg. Chim. Acta 363 (2010) 2425.
[14] Q.H. Jin, L.M. Chen, L. Yang, S.F. Deng, R. Wang, Inorg. Chim. Acta. 362 (2009)
1743.
[15] B.J. Prince, M.M. Turnbull, R.D. Willett, J. Coord. Chem. 56 (2003) 441.
[16] Y. Cui, H.J. Mo, J.C. Chen, Y.L. Niu, Y.R. Zhong, K.C. Zheng, B.H. Ye, Inorg. Chem.
46 (2007) 6427.
[17] H.J. Mo, Y.L. Niu, M. Zhang, Z.P. Qiao, B.H. Ye, Dalton Trans. 40 (2011) 8218.
[18] G.M. Sheldrick, SHELXS-97 and SHELXL-97, Software for Crystal Structure Analysis,
Siemens Analytical X-ray Instruments Ins, Wisconsin, Madison, USA, 1997.
[19] G.M. Sheldrick, SHELXTL NT Version 5.1. Program for Solution and Refinement of
Crystal Structures, University of Göttingen, Germany, 1997.
[20] Q.H. Jin, K.Y. Hu, L.L. Song, R. Wang, C.L. Zhang, X. Zuo, X.M. Lu, Polyhedron 29
(2010) 441.
Seven copper(I) complexes of ADMT have been synthesized and
characterized by NMR, luminescence, X-ray diffraction for the first
time. The structures of 1–7 are controlled by synergistic function
among metals and N- and P- (As-) donor ligands, as well as by
intramolecular hydrogen bonds N-HÁÁÁX (X = Cl, Br) and intermolec-
ular hydrogen bonds R22(8). 1, 2, 5 and 6 form infinite zigzag chain
by intramolecular hydrogen bonds N–HÁÁÁX and intermolecular
hydrogen bonds R22(8). Complexes 3 and 4 contain the intramolec-
ular hydrogen bond R11(6) N–HÁÁÁX while 5 contains the intermo-
lecular hydrogen bond R22(8) to form a dimer. Hydrogen bonds
not only stabilize Cu(I) complexes but also control their final
structures.
Acknowledgements
This work has been supported by the National Natural Science
Foundation of China (grant No. 21171119), the National High Tech-
nology Research and Development Program 863 of China
(2012AA063201), the Committee of Education of the Beijing Foun-
dation of China (grant No. KM201210028020), Program for Excel-
lent Talents of Beijing City (grant no. 2010D005016000002).
Beijing Municipal Natural Science Foundation (grant no. 7122015).
[21] J. Lu, G. Crisci, T. Niu, A.J. Jacobson, Inorg. Chem. 36 (1997) 5140.
[22] A. Turco, C. Panattoni, E. Frasson, Nature 187 (1960) 772.
[23] P.G. Owston. J.M. Rowe, Acta Cryst. 13 (1960) 253.
[24] C.X. Ruan, W.J. Shi, Acta Crystallog. E 63 (9) (2007) m2412.
[25] M. Dennehy, G.P. Telleria, O.V. Quinzani, G.A. Echeverria, O.E. Piro, E.E.
Castellano, Inorg. Chim. Acta. 362 (2009) 2900.
[26] J.T. Gill, J.J. Mayerle, P.S. Welcker, D.F. Lewis, D.A. Ucko, D.J. Barton, D. Stowens,
S.J. Lippard, Inorg. Chem. 15 (1976) 1155.
[27] R.D. Hart, J.D. Kildea, C. Pettinari, B.W. Skelton, Inorg. Chim. Acta 359 (2006)
2178.
[28] C.X. Ding, X. Li, Y.B. Ding, X. Li, S.W. Ng, Y.S. Xie, Cryst. Growth Des. 12 (2012)
3465.
Appendix A. Supplementary data
[29] Y.Y. Tang, C.X. Ding, S.W. Ng, Y.S. Xie, RSC Adv. 3 (2013) 10184.
[30] Y.L. Xiao, Q.H. Jin, Y.H. Deng, Z.F. Li, W. Yang, M.H. Wu, C.L. Zhang, Inorg. Chem.
Commun. 15 (2012) 146.
[31] A. Tsuboyama, K. Kuge, M. Furugori, S. Okada, M. Hoshino, K. Ueno, Inorg.
Chem. 46 (2007) 1992.
CCDC 965342 (complex 1), 944737 (complex 2), 944738 (com-
plex 3), 976863 (complex 4), 965344 (complex 5) 965345 (com-
plex 6) and 976864 (complex 7) contains the supplementary
crystallographic data for this paper. These data can be obtained